- Preparation method of E-1, 3, 3, 3-tetrafluoropropene
-
The invention discloses a preparation method of E-1, 3, 3, 3-tetrafluoropropene, which comprises the following steps: by taking 3, 3, 3-trifluoropropyne or/and an isomer 1, 3, 3-trifluoropropadiene thereof as a raw material, carrying out gas-phase selective fluorination reaction in the presence of a fluorination catalyst to obtain E-1, 3, 3, 3-tetrafluoropropene. The method provided by the invention is mainly used for producing E-1, 3, 3, 3-tetrafluoropropene in a high-efficiency and gas-phase continuous circulation manner.
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Paragraph 0033-0034
(2021/05/19)
-
- Preparation method of Z-1-halogen-3, 3, 3-trifluoropropene
-
The invention discloses a preparation method of Z-1-halogen-3, 3, 3-trifluoropropene. The preparation method comprises the following steps: in the presence of a block catalyst, E-1-halogen-3, 3, 3-trifluoropropene is subjected to a gas phase isomerization reaction in a tubular reactor to obtain Z-1-halogen-3, 3, 3-trifluoropropene, and halogen is fluorine or chlorine. According to the preparation method, 1, 1, 1, 3, 3-pentachloropropane is used as an initial raw material, Z-1-chloro-3, 3, 3-trifluoropropene or Z-1, 3, 3, 3-tetrafluoropropene secondary product is prepared through a gas-phase fluorination reaction and an isomerization reaction, the materials which are not completely reacted are independently circulated through a gas-phase independent circulation process so that the initial raw materials can be almost completely converted into the target product, and finally, the target product is extracted from a process system, and thus liquid waste and waste gas are not generated, and green production is realized.
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Paragraph 0042-0043; 0046
(2021/05/01)
-
- Method for preparing 3, 3, 3-trifluoropropyne through gas-phase dehydrohalogenation
-
The invention discloses a method for preparing 3, 3, 3-trifluoropropyne through gas-phase dehydrohalogenation. The method comprises the following steps: taking 1-halogen-3, 3, 3-trifluoropropene or/and 2-halogen-3, 3, 3-trifluoropropene (halogen = F or Cl or Br or I) as a raw material, and carrying out gas-phase dehydrohalogenation reaction in the presence of a catalyst to obtain the 3, 3, 3-trifluoropropyne. The method disclosed by the invention is mainly used for producing the 3, 3, 3-trifluoropropyne in a gas-phase continuous circulation manner at a high conversion rate and high selectivity.
- -
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Paragraph 0040-0041; 0046-0049
(2021/06/23)
-
- Preparation method of E-1-halogen-3, 3, 3-trifluoropropene
-
The invention discloses a preparation method of E-1-halogen-3, 3, 3-trifluoropropene. The preparation method comprises the following steps: in the presence of a block catalyst, carrying out gas-phase fluorination reaction on 1, 1, 1, 3, 3-pentachloropropane and hydrogen fluoride in a tubular reactor to obtain a main product E-1-chlorine-3, 3, 3-trifluoropropene and a small amount of product Z-1-chlorine-3, 3, 3-trifluoropropene; furthermore, in the presence of the block catalyst, E-1-chlorine-3, 3, 3-trifluoropropene or/and Z-1-chlorine-3, 3, 3-trifluoropropene and hydrogen fluoride are subjected to a gas-phase fluorination reaction in the tubular reactor, and a main product E-1, 3, 3, 3-tetrafluoropropene is obtained. The one-way yield of the method is high; especially for the second-step process, only HCl in the product flow in the first step needs to be removed, and the remaining substances can be directly used for fluorination reaction after new HF is added. The block catalyst has the characteristics of high activity and long service life.
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Paragraph 0052
(2021/05/01)
-
- HFO-1234yf as a CF3-Building Block: Synthesis and Chemistry of CF3-Ynones
-
Reaction of low cost, readily available 4th generation refrigerant gas 2,3,3,3-tetrafluoropropene (HFO-1234yf) with lithium diisopropylamide (LDA) leads to formation of lithium 3,3,3-trifluoropropynide, addition of which to a range of aldehydes formed CF3-alkynyl alcohol derivatives on multigram scale, which were oxidised using Dess–Martin periodinane (DMP) to give substituted CF3-ynones with minimal purification required. Michael-type additions of alcohol and amine nucleophiles to CF3-ynones are rapid and selective, affording a range of CF3-enone ethers and enaminones in excellent yields with high stereoselectivity for the Z-isomer. By analogous reactions with difunctional nucleophiles, a wide range of CF3-substituted pharmaceutically relevant heterocyclic structures can be accessed, exemplified in the simple synthesis of the anti-arthritis drug celecoxib from HFO-1234yf in just three steps.
- Murray, Ben J.,Marsh, Thomas G. F.,Yufit, Dmitri S.,Fox, Mark A.,Harsanyi, Antal,Boulton, Lee T.,Sandford, Graham
-
supporting information
p. 6236 - 6244
(2020/09/15)
-
- METHOD FOR PRODUCING FLUOROCARBON USING HYDROHALOFLUOROPROPENE
-
PROBLEM TO BE SOLVED: To provide a method for selectively producing fluorocarbon by efficiently isomerizing a hydrofluoropropene isomer (isomer 1) under the reduction of catalytic performance to produce a corresponding hydrohalofluoropropene isomer (isomer 2) and using the same. SOLUTION: Provided is a method for producing 3,3,3-trifluoropropene by contacting a 1-halogeno-3,3,3-trifluoropropene isomer with a moisture concentration of 100 ppm or lower (isomer 1) in a vapor phase so as to be isomerized to produce a corresponding 1-halogeno-3,3,3-trifluoropropene isomer (isomer 2), and subjecting the 1-halogeno-3,3,3-trifluoropropene isomer (isomer 2) to dehalogenation. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2018,JPOandINPIT
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-
Paragraph 0259
(2018/07/31)
-
- METHOD FOR PRODUCING FLUORINE-CONTAINING ALKYNE COMPOUND
-
PROBLEM TO BE SOLVED: To provide a fluorine-containing alkyne compound in a manner that is convenient and easy to scale up. SOLUTION: The present invention provides a method for producing a fluorine-containing alkyne compound represented by general formula (1): RfC≡CH (1) [where Rf is a fluorine-containing alkyl group], the method including the steps of causing a compound represented by general formula (2): RfCH=CX1 CR2 OH (2) [where Rf is the same as above. X1 is a halogen atom. R's are the same or different to represent a hydrogen atom or an alkyl group] to react with a base at 50°C or more. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
- -
-
Paragraph 0047; 0050
(2019/01/08)
-
- PROCESS FOR THE PREPARATION OF TETRAFLUOROPROPENE
-
A process for producing at least one tetrafluoropropene, the process comprising (i) converting Z-1233zd to TFMA in the presence of at least one base, wherein the process is conducted in the presence of water, and (ii) contacting the TFMA produced in step (i) with hydrogen fluoride (HF) in the presence of a Lewis acid metal halide catalyst to produce reaction product comprising at least one tetrafluoropropene.
- -
-
Page/Page column 8
(2016/09/15)
-
- One-Step Process for Hexafluoro-2-Butene
-
Disclosed is a one step process for making of 1,1,1,4,4,4-hexafluoro-2-butene. More specifically, the present invention provides a process for making hexafluoro-2-butene, continuously, from 2-chloro-3,3,3-trifluoropronene using Fe2O3/NiO impregnated carbon catalyst at 600° to 650° C.
- -
-
Paragraph 0035; 0036
(2016/02/18)
-
- Method for producing 3, 3, 3 - [...]
-
PROBLEM TO BE SOLVED: To provide a method for producing 3,3,3-trifluoropropyne easily executable on an industrial scale and also at a low cost.SOLUTION: (Z)-1-chloro-3,3,3-trifluoropropyne obtained by various production methods is continuously or semicontinuously contacted with the hydroxide of an alkali metal in the presence of water, and the produced 3,3,3-trifluoropropyne is continuously drawn out from the reaction system.
- -
-
Paragraph 0208-0211
(2017/06/02)
-
- DEHALOGENATION OF TRANS-1-CHLORO-3,3,3-TRIFLUOROPROPENE
-
The present invention is related to making hydrofluorocarbons (HCFCs), more specifically, 3,3,3-trifluoropropyne (TFP), from trans-1-chloro-3,3,3-trifluoropropene (trans-1233zd) by contacting the trans-1233zd with a base. Preferably, the base is potassium hydroxide or potassium tert-butoxide, which may or may not be dissolved in as solvent.
- -
-
Paragraph 0021-0024
(2014/12/09)
-
- METHODS FOR PRODUCING 1-CHLORO-3,3,3-TRIFLUOROPROPENE FROM 2-CHLORO-3,3,3-TRIFLUOROPROPENE
-
The present invention provides processes for the production of HCFO-1233zd, 1-chloro-3,3,3-trifluoropropene, from the starting material, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). In a first process, HCFO-1233zd is produced by the isomerization of HCFO-1233xf. In a second process, HCFO-1233zd is produced in a two-step procedure which includes (i) dehydrochlorination of HCFO-1233xf into trifluoropropyne; and (ii) hydrochlorination of the trifluoropropyne into HCFO-1233zd.
- -
-
Paragraph 0040
(2013/12/03)
-
- HIGH PURITY E-1-CHLORO-3,3,3-TRIFLUOROPROPENE AND METHODS OF MAKING THE SAME
-
The present invention discloses high purity E-1-chloro-3,3,3-trifluoropropene (1233zd(E)) and methods to produce the same. More specifically, the present invention discloses the methods of making 1233zd(E) essentially free of toxic impurities (e.g. 2-chloro-3,3,3-trifluoropropene (1233xf), chlorotetrafluoro-propene (1224), and 3,3,3-trifluoropropyne). The present invention further provides methods for making high purity 1233zd(E) with concentration of 1233xf and 1224 at or below 200 parts per million (ppm) and 3,3,3-trifluoropropyne impurities at or below 20 ppm. Formation of 1233xf impurity can be avoided if pure 1,1,1,3,3-pentachloropropane is used as a starting material. It was also found that formation of 1233xf is avoided if a liquid phase manufacturing process is used.
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-
Page/Page column 4-5
(2012/07/14)
-
- Reactions of fluoroalk-1-en-1-yltrifluoroborate and perfluoroalk-1-yn-1- yltrifluoroborate salts and selected hydrocarbon analogues with hydrogen fluoride and with halogenating agents in aHF and in basic solvents
-
The relative rate of the electrophilic hydrodeboration of K[R′BF 3] with HF (27-100%) diminishes in the series R′ = C 4H9CC > C4F9CFCFCC > CF 2C(CF3) > C3F7CC ~ (CF 3)2CFCC > CF3CC. When R′ = CF 3CC the new salt K[CF3CH2-CF2BF 3] was obtained by addition of HF besides CF3CCH and K[BF4]. Small amounts of water caused the formation of K[CF 3CH2-C(O)BF3] as a by-product. The electrophilic halofluorination of perfluoroalkenyltrifluoroborate salts with NCS or NBS in aHF (anhydrous HF) led to K[RFCFHal-CF2BF 3] (from K[RFCFCFBF3]) and K[R FCHal2-CF2BF3] (from K[R FCHalCFBF3] and K[RFCCBF3]) (Hal = Cl, Br). Treatment of K[RFCFCFBF3] and K[R FCCBF3] with 5% F2/N2 in MeCN gave the corresponding salts K[RFCF2-CF2BF 3] in 16-25% isolated yield. Reactions of K[trans-C4F 9CFCFBF3] with Cl2 in MeOH resulted in K[C 4F9CFCl-C(O)BF3] (major product). The latter was also obtained in reactions of K[trans-C4F9CFCFBF 3] with Cl2 in MeCN or sulfolane after sequential methanolysis of the primarily formed products. In contrast, the salts K[RCFCFBF3] (R = CnF2n+1, trans-C 4H9) and K[CF3CCBF3] underwent bromodeboration to RCFCFBr and CF3CCBr, respectively, when they were reacted with bromine in the polar solvents MeOH, MeCN, or sulfolane.
- Bardin, Vadim V.,Adonin, Nicolay Yu.,Frohn, Hermann-Josef
-
experimental part
p. 114 - 128
(2012/04/10)
-
- β-(trifluoromethyl)vinyl sulfonium salts: Preparation and reactions with active methylene and methenyl compounds
-
Two trifluoromethyl-substituted building blocks β-(trifluoromethyl) vinyl sulfonium salts 1 and 2 were developed. Reactions of β- (trifluoromethyl)vinyl sulfonium salt 1 with active methylene compounds containing electron-withdrawing groups using DBU as the base in DMSO occurred to give trifluoromethyl-substituted cyclopropane derivatives 7 as the major products. In contrast, reactions of β-(trifluoromethyl)vinyl sulfonium salt 2 with active methylene compounds occurred with the migration of one of the electron-withdrawing groups to give the products 8 as the major products when NaH was used as the base in DMSO. Moreover, when NaH was used as base in THF/CH2Cl2 at -78 °C, reaction of β- (trifluoromethyl)vinyl sulfonium salt 1 gave trifluoromethyl-substituted 2,3-dihydrofuran derivatives 9 as the major products. A working mechanism was proposed to explain the different behaviors of the β-(trifluoromethyl)vinyl sulfonium salts 1 or 2 with active methylene compounds under these different conditions.
- Lin, Hao,Shen, Qilong,Lu, Long
-
supporting information; experimental part
p. 7359 - 7369
(2011/11/06)
-
- Design and synthesis of novel N-hydroxy-dihydronaphthyridinones as potent and orally bioavailable HIV-1 integrase inhibitors
-
Figure Presented. HIV-1 integrase (IN) is one of three enzymes encoded by the HIV genome and is essential for viral replication, and HIV-1 IN inhibitors have emerged as a new promising class of therapeutics. Recently, we reported the synthesis of orally bioavailable azaindole hydroxamic acids that were potent inhibitors of the HIV-1 IN enzyme. Here we disclose the design and synthesis of novel tricyclic N-hydroxy-dihydronaphthyridinones as potent, orally bioavailable HIV-1 integrase inhibitors displaying excellent ligand and lipophilic efficiencies.
- Johnson, Ted W.,Tanis, Steven P.,Butler, Scott L.,Dalvie, Deepak,Delisle, Dorothy M.,Dress, Klaus R.,Flahive, Erik J.,Hu, Qiyue,Kuehler, Jon E.,Kuki, Atsuo,Liu, Wen,McClellan, Guy A.,Peng, Qinghai,Plewe, Michael B.,Richardson, Paul F.,Smith, Graham L.,Solowiej, Jim,Tran, Khanh T.,Wang, Hai,Yu, Xiaoming,Zhang, Junhu,Zhu, Huichun
-
experimental part
p. 3393 - 3417
(2011/07/08)
-
- PROCESS FOR PREPARING FLUORINE-CONTAINING ALKYNE COMPOUND
-
The present invention provides a process for producing a fluorine-containing alkyne compound represented by the formula: wherein Rf is a fluorine-containing alkyl group, the process including subjecting a fluorine-containing alkene compound represented by the formula: RfCX=CHY, wherein Rf is a fluorine-containing alkyl group, and one of X and Y is a halogen atom, and the other is a hydrogen atom, to a dehydrohalogenation reaction in a gas phase in the presence of at least one compound selected from the group consisting of alkali metal- or alkaline earth metal-containing halides; alkali metal- or alkaline earth metal-containing oxides; and alkali metal- or alkaline earth metal-containing hydroxides. This process can produce a fluorine-containing alkyne compound, such as 3,3,3-trifluoropropyne, with a high selectivity in a relatively simple manner.
- -
-
Page/Page column 7-9
(2010/09/17)
-
- PROCESS FOR PREPARING 2,3,3,3-TETRAFLUOROPROPENE
-
The present invention provides a process for preparing 2,3,3,3-tetrafluoropropene comprising the steps of: (a) reacting 3,3,3-trifluoropropyne with hydrogen fluoride while heating to obtain a product containing 2,3,3,3-tetrafluoropropene; (b) separating the product obtained in Step (a) into Component A containing 2,3,3,3-tetrafluoropropene and 3,3,3-trifluoropropyne, and Component B containing 1,3,3,3-tetrafluoropropene; (c) separating 2,3,3,3-tetrafluoropropene and 3,3,3-trifluoropropyne contained in Component A obtained in Step (b) into each compound; (d) conducting a dehydrofluorination reaction by heating Component B obtained in Step (b) in the presence of a catalyst; (e) separating the product obtained in Step (d) into Component C containing 2,3,3,3-tetrafluoropropene and 3,3,3-trifluoropropyne, and Component D containing 1,3,3,3-tetrafluoropropene; (f) separating 2,3,3,3-tetrafluoropropene and 3,3,3-trifluoropropyne contained in Component C obtained in Step (e) into each compound; and (g) conducting a dehydrofluorination reaction by heating Component D obtained in Step (e) in the presence of a catalyst. The present invention provides an effective and industrially applicable process for preparing 2,3,3,3-tetrafluoropropene.
- -
-
Page/Page column 20; 22
(2010/05/14)
-
- METHOD FOR PRODUCING 3,3,3-TRIFLUOROPROPYNE
-
Disclosed is a method for producing 3,3,3-trifluoropropyne, which is characterized in that a base is reacted with (Z)-1-halogeno-3,3,3-trifluoropropene represented by formula [1]. It is possible by this production method to obtain 3,3,3-trifluoropropyne with high yield. Furthermore, since waste disposal is also easy, it is a production method that is industrially advantageous.
- -
-
Page/Page column 7
(2010/01/29)
-
- Unusual behavior of the anionic species from (E)-1-chloro-3,3,3- trifluoropropene(HCFC-1233t)
-
(E)-1-Chloro-3,3,3-trifluoropropene was smoothly deprotonated by MeLi at the position β to the CF3 group, and exclusive formation of propargylic alcohols was observed by addition of appropriate carbonyl compounds as long as up to 1.6 equiv. of
- Miyagawa, Akiko,Naka, Motoki,Yamazaki, Takashi,Kawasaki-Takasuka, Tomoko
-
body text
p. 4395 - 4399
(2010/01/07)
-
- METHOD FOR PRODUCING 1,3,3,3-TETRAFLUOROPROPENE
-
There is provided a method for producing 1,3,3,3-tetrafluoropropene by subjecting 1,1,1,3,3-pentafluoropropane to a dehydrofluorination reaction in gas phase in the presence of a catalyst, the method for producing 1,3,3,3-tetrafluoropropene being characterized in that there is used a zirconium compound-carried catalyst in which a zirconium compound is carried on a metal oxide or activated carbon.
- -
-
Page/Page column 6
(2009/04/23)
-
- TWO STEP PROCESS FOR THE MANUFACTURE OF HYDROFLUOROOLEFINS
-
The present invention discloses a process for the synthesis of hydrofluoroolefins (HFO). The process is based on the following two steps: the liquid phase fluorination of a hydrochloropropane(s) to hydrofluoropropane(s) (HFP) followed by the dehydrofluorination of the hydrofluoropropane(s) (HFP) to hydrofluoroolefins (HFO).
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-
Page/Page column 15-16
(2009/03/07)
-
- Fluorinated acetylenes. Part 8. Preparation and some reactions of 5,5,5-trifluoropent-3-yn-2-ol, 5,5,5-trifluoro-1-phenylpent-3-yn-2-ol and the derived ester, 2-acetoxy-5,5,5-trifluoropent-3-yne
-
Treatment of the salt CF3CCLi (3) with the aldehydes RCH2CHO (R = H and Ph) affords the secondary alcohols CF3CCCHROH (1a) R = Me and (1b) R = CH2Ph.Alcohol 1a does not give the corresponding ketone on attempted oxidation (pyridinium chlorochromate or Na2Cr2O7/H2SO4), but alcohol 1b is oxidized to the diketone (CF3CCCOCHPh)2 (7) (41percent) by active MnO2.The acetate CF3CCCHMeO2CMe (2) undergoes facile reaction with diazomethane to give 3--1-methyl-4-trifluoromethylpyrazole (10a) and hence the 3- and 5--1-methyl-4-trifluoromethylpyrazoles (11a) and (12a), respectively.Cycloaddition also takes place between ester 2 and furan, but the major products (considered to be isomeric 1:1 adducts) have not been fully characterised.Although, ester 2 undergoes reaction with trifluoronitrosomethane, a cycloadduct has not been isolated, while nucleophilic attack by imidazole on the triple bond leads to the (Z)-alkene (18).
- Sibous, Lakhdar,Tipping, Anthony E.
-
-
- FLUORINATED ACETYLENES. PART 7. PREPARATION AND SOME REACTIONS OF 4,4,4-TRIFLUOROBUT-2-YNOIC ACID AND 1-PHENYL-4,4,4-TRIFLUOROBUT-2-YN-1-OL
-
Treatment of the salt CF3C CLi with alkyl chloroformates affords the compounds CF3C CCO2R (R=Et and CH2Ph) in relatively low yield and with gaseous carbon dioxide yields the acid CF3C CCO2H.Reaction of the acid with diazomethane gives the methyl ester which, with an excess of the reagent, undergoes regiospecific 1,3-dipolar cycloaddition to produce 3-carbomethoxy-4-trifluoromethylpyrazole and hence the 3- and 5-carbomethoxy-1-methyl-4-trifluoromethylpyrazoles.Oxidation of the alcohol CF3C CCH(OH)Ph (active MnO2) affords a 70:23 mixture of 3-benzoyl-2,4-bis(trifluoromethyl)-2-hydroxy-6-phenyl-α-pyran and E-1,3-dibenzoyl-2-trifluoromethylpropene (via the ketone CF3C CCOPh).
- Tajammal, Sabiha,Tipping, Anthony E.
-
-
- Laser-Induced Reactions of Hexafluorobenzene and Selected Hydride Compounds
-
Infrared-laser-induced reactions between C6F6 and general hydrides R-H (R = H, D, CH3, HCC, H2C=CH, and Cl) were studied by irradiating C6F6 at 1027 cm-1 in C6F6/R-H mixtures.In general, two competitive pathways involving C-F bond cleavage in C6F6 were observed as follows: (1) C6F6 + R-H C6F5H + R-F and (2) C6F6 + R-H C6F5R + HF.C6F6 decomposition also took place to a minor extent depending on the mole fraction of C6F6 and gave rise to C2F4 and C2H2.From infrared and GC/MS analysis of the product mixtures after 20-200 pulses, C6F5H was observed in all reactions except that involving D2.When D2 was used C6F5D was the major product.C6F5H was the major product in the reactions involving H2 and C2H2.In the reaction with C2H4, C6F5H was the major product derived from C6F6 though C2H2 was the major product of the reaction.The large amount of C2H2 seems to be derived from an additional sensitized decomposition of C2H4.C6F5H was present in minor amounts in the reaction with CH4 and HCl.Besides C6F5H, other monosubstituted products derived from C6F6 were also formed, generally within 20-100 pulses.Thus, C6F5CH3, C6F5CH=CH2, C6F5CCH, and C6F5Cl were produced, respectively, in the reaction of C6F6 with CH4, C2H4, C2H2, and HCl.In the first and last cases these products were the major ones observed.The results are discussed mechanistically in terms of the initial formation of the C6F5. radical and synthetically in terms of the utility of obtaining selective-laser-induced reduction of C6F6.
- Koga, Yoshinori,Chen, Ruth,Keehn, Philip M.
-
p. 306 - 311
(2007/10/02)
-
- ARYL TRIFLUOROMETHYL ACETYLENES
-
A wide variety of aryl trifluoromethyl acetylenes may be prepared in high yield by allowing CF3CCZnCl, generated from CF3CCH, to react with aryl iodides and a catalytic amount of tetrakis(triphenylphosphine)palladium
- Bunch, J. E.,Bumgardner, C. L.
-
p. 313 - 318
(2007/10/02)
-
- Rates of Base-Catalyzed Hydrogen Exchange of Terminal Acetylenes in Aqueous Solution. Absence of Resonance Interaction
-
Rates of detritiation of 13 monosubstituted acetylenes labeled at the acetylenic hydrogen position were measured in aqueous amine buffer solution at 25 deg C, and hydroxide ion catalytic coefficients were evaluated.These rate constants, plus a few additional values from the literature, give a good correlation against inductive or field substituent constants: log(kHO-/M-1s-1) = 1.46+/-0.12 + (8.00+/-0.50)?I.This correlation is not improved by addition of resonance substituted constants, and the coefficients of the resonance term in two different dual parameter (resonance plus field) treatments of the data are in fact zero.
- Kresge, A. J.,Powell, M. F.
-
p. 819 - 822
(2007/10/02)
-
- REACTION OF THE SALTS OF DITHIO ACIDS WITH TRIFLUOROMETHYLACETYLENE AND TRIFLUOROMETHYLALKYLDIACETYLENES
-
The reactions of the triethylammonium salts of N,N-diethyl- and N-piperidinodithiocarbamic and 2-thiophenedithiocarboxylic acids with trifluoromethylacetylene and trifluoromethylisopropyl- and trifluoromethyl-tert-butyldiacetylenes were investigated.With trifluoromethylacetylene and trifluoromethylalkyldiacetylenes the dithiocarbamate salts form the Z adducts from nucleophilic addition.Unlike the dithiocarbamates, the 2-thiophenediethiocarboxylate salt forms the product from 1,3-anionic cycloaddition exclusively with trifluoromethylisopropyldiacetylene and both the product from 1,3-anio nic cycloaddition and the product from nucleophilic addition with trifluoromethylacetylene.
- Stepanova, N. P.,Kuz'mina, N. Ya.,Turbanova, E. S.,Petrov, M. L.
-
p. 1667 - 1670
(2007/10/02)
-
- NEW FLUORIDE ION-CATALYZED REACTION OF F-ALKYLACETYLENES WITH SILYL ENOL ETHERS. AN EFFICIENT ROUTE TO F-ALKYL-SUBSTITUTED PROPAPGYLIC ALCOHOLS AND α-HYDROXY KETONES
-
Treatment of F-alkylacetylenes, generated in situ from 1H-F-1-alkenephosphonates, with silyl enol ethers in the presence of a catalytic amount of tetrabutylammonium fluoride gives good yields of F-alkyl-substituted propargyl alcohols or 4-(1H-F-alkylidene)-1,3-dioxolane derivatives, the latter being converted to the corresponding α-hydroxy ketones.
- Ishihara, Takashi,Yamasaki, Yasuhiro,Ando, Teiichi
-
-
- HETEROCYCLIC POLYFLUORO-COMPOUNDS. PART 35. DEHYDROFLUORINATION OF 2,2-BIS(TRIFLUOROMETHYL)- AND 2-PERFLUOROALKYL-3,4-DIFLUORO-OXETANS
-
Solid potassium hydroxide dehydrofluorinates 2,2-bis-(trifluoromethyl)-3,4-difluoro-oxetan to 3-fluoro-4,4-bis-(trifluoromethyl)-2-oxete (59percent), 2-pentafluoroethyl-3,4-difluoro-oxetan to 2-tetrafluoroethylidene-3,4-difluoro-oxetan, and r-2-heptafluoro-n-propyl-t-3,t-4-difluoro-oxetan to (Z)-2-hexafluoro-n-propylidene-cis-3,4-difluoro-oxetan.Factors which affect these reactions are discussed.
- Barlow, M. G.,Coles, B.,Haszeldine, R. N.
-
p. 387 - 396
(2007/10/02)
-